U.S. patent application number 14/141880 was filed with the patent office on 2014-07-03 for method for inkjet textile printing.
This patent application is currently assigned to MATSUI SHIKISO CHEMICAL CO., LTD.. The applicant listed for this patent is MATSUI SHIKISO CHEMICAL CO., LTD.. Invention is credited to Daisuke INOUE, Masaki KARIYA, Yosuke KITAGAWA.
Application Number | 20140186533 14/141880 |
Document ID | / |
Family ID | 51017485 |
Filed Date | 2014-07-03 |
United States Patent
Application |
20140186533 |
Kind Code |
A1 |
KITAGAWA; Yosuke ; et
al. |
July 3, 2014 |
METHOD FOR INKJET TEXTILE PRINTING
Abstract
Method for inkjet textile printing comprising a printing step
for printing an aqueous pigment ink on a specifically pretreated
portion of a textile fiber product by an inkjet process, wherein
said specific pretreatment is performed by applying at least: (A) a
quaternary ammonium salt type cationic surfactant represented by
the formula (1) below, and (B) a block isocyanate compound to the
entire textile fiber product or a required portion thereof, and
said aqueous pigment ink comprises at least a pigment, an aqueous
liquid as a solvent or dispersion medium, and: (C) a water-soluble
dispersing agent having a crosslinking property, (D) a
self-emulsifying type urethane resin, and (E) a block isocyanate
compound. ##STR00001## [Two of R.sup.1 to R.sup.4: alkyl having 8
to 18 carbon atoms; the remaining two: methyl or ethyl; X.sup.-:
anion.]
Inventors: |
KITAGAWA; Yosuke; (KYOTO,
JP) ; KARIYA; Masaki; (KYOTO, JP) ; INOUE;
Daisuke; (KYOTO, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
MATSUI SHIKISO CHEMICAL CO., LTD. |
Kyoto |
|
JP |
|
|
Assignee: |
MATSUI SHIKISO CHEMICAL CO.,
LTD.
Kyoto
JP
|
Family ID: |
51017485 |
Appl. No.: |
14/141880 |
Filed: |
December 27, 2013 |
Current U.S.
Class: |
427/288 |
Current CPC
Class: |
D06P 5/30 20130101; D06P
1/6424 20130101; D06P 1/5285 20130101; D06P 1/66 20130101 |
Class at
Publication: |
427/288 |
International
Class: |
D06P 3/02 20060101
D06P003/02 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 28, 2012 |
JP |
2012-287504 |
Claims
1. A method for inkjet textile printing comprising a printing step
for printing an aqueous pigment ink on a specifically pretreated
portion of a textile fiber product by an inkjet process, wherein
said specific pretreatment is performed by applying at least: (A) a
quaternary ammonium salt type cationic surfactant represented by
the formula (1) below, and (B) a block isocyanate compound to the
entire textile fiber product or a required portion thereof, and
said aqueous pigment ink comprises at least a pigment, an aqueous
liquid as a solvent or dispersion medium, and: (C) a water-soluble
dispersing agent having a crosslinking property, (D) a
self-emulsifying type urethane resin, and (E) a block isocyanate
compound. ##STR00003## [In the formula (1), two of R.sup.1 to
R.sup.4 mutually independently represent an alkyl group having 8 to
18 carbon atoms, the remaining two mutually independently represent
a methyl group or an ethyl group, and X.sup.- represents an
anion.]
2. The method for inkjet textile printing according to claim 1
having a pretreatment step for performing the specific pretreatment
on the entire textile fiber product or a required portion thereof
prior to said printing step.
3. The method for inkjet textile printing according to claim 1
wherein the pretreatment is performed by applying a pretreatment
agent containing at least: (A) a cationic surfactant represented by
the formula (1) and (B) a block isocyanate compound to the entire
textile fiber product or a required portion thereof.
4. The method for inkjet textile printing according to claim 1
wherein (B) the block isocyanate compound is a compound resulting
from blocking of the isocyanate group in trimethylolpropane adduct
form or isocyanurate form of: hexamethylene diisocyanate,
hydrogenated xylylene diisocyanate, isophorone diisocyanate, or
dicyclohexylmethane diisocyanate.
5. The method for inkjet textile printing according to claim 4
wherein (B) the block isocyanate compound has been obtained using
diethyl malonate, diisopropylamine, 1,2,4-triazole,
3,5-dimethylpyrazole, or 2-butanonoxime as a blocking agent.
6. The method for inkjet textile printing according to claim 1
wherein the aqueous pigment ink is a dispersion liquid containing a
dispersed pigment having a maximum particle diameter of not more
than 500 nm.
7. The method for inkjet textile printing according to claim 1
wherein (C) the water-soluble dispersing agent having a
crosslinking property results from neutralization, with a basic
substance, of an emulsion polymer having a molecular weight of
2,000 to 20,000 obtained from: (1) 20 to 80 parts by weight of a
(meth)acrylic acid ester monomer represented by
CH.sub.2.dbd.CR.sup.5--COOR.sup.6 [wherein R.sup.5 represents a
hydrogen atom or a methyl group, and R.sup.6 represents an alkyl
group having 2 to 8 carbon atoms.], (2) 80 to 20 parts of an
aliphatic vinyl monomer having a carboxyl group, and (3) 0 to 20
parts of an aliphatic vinyl monomer having a crosslinking
property.
8. The method for inkjet textile printing according to claim 7
wherein (2) the aliphatic vinyl monomer having a carboxyl group is
at least one selected from the group consisting of acrylic acid,
methacrylic acid, itaconic acid, maleic acid, and fumaric acid.
9. The method for inkjet textile printing according to claim 7
wherein the basic substance is a secondary amine or a tertiary
amine.
10. The method for inkjet textile printing according to claim 1
wherein the blending ratio of (C) the water-soluble dispersing
agent having a crosslinking property in the aqueous pigment ink
ranges from 0.05 to 2.0 parts by weight relative to 1.0 part by
weight of the pigment.
11. The method for inkjet textile printing according to claim 1
wherein the aqueous pigment ink contains a polyoxyethylene
styrenated phenyl ether sulfate or a polyoxyethylene alkyl ether
sulfate as a dispersing aid.
12. The method for inkjet textile printing according to claim 1
wherein (D) the self-emulsifying type urethane resin has been
obtained from a composition comprising at least: an isocyanate and
a polyol having a carboxyl group or a sulfonic acid group.
13. The method for inkjet textile printing according to claim 1
wherein the glass transition point (Tg) of (D) the self-emulsifying
type urethane resin is -60 to 20.degree. C.
14. The method for inkjet textile printing according to claim 1
wherein (E) the block isocyanate compound is a compound resulting
from blocking the isocyanate group in trimethylolpropane adduct
form or isocyanurate form of: hexamethylene diisocyanate,
hydrogenated xylylene diisocyanate, isophorone diisocyanate, or
dicyclohexylmethane diisocyanate.
15. The method for inkjet textile printing according to claim 14
wherein (E) the block isocyanate compound has been obtained with
diethyl malonate, diisopropylamine, 1,2,4-triazole,
3,5-dimethylpyrazole, or 2-butanonoxime as a blocking agent.
16. The method for inkjet textile printing according to claim 1
wherein (E) the block isocyanate compound is water-soluble or
self-emulsifying, and wherein the aqueous pigment ink is
excellently redispersible.
17. The method for inkjet textile printing according to claim 1
wherein the viscosity of the aqueous pigment ink is 3 to 30 mPas at
20.degree. C.
18. The method for inkjet textile printing according to claim 1
wherein the surface tension of the aqueous pigment ink is 20 to 40
mN/m.
19. The method for inkjet textile printing according to claim 1,
having a heat treatment step for heating at least a portion on
which an aqueous pigment ink is printed of a textile fiber product
on which the aqueous pigment ink is printed by an inkjet process in
said printing step.
20. The method for inkjet textile printing according to claim 2
wherein the pretreatment is performed by applying at least: (A) a
cationic surfactant represented by the formula (1) above and (B) a
block isocyanate compound to the entire textile fiber product or a
required portion thereof by a padding process, coating process,
screen printing process, inkjet process, or spraying process.
21. The method for inkjet textile printing according to claim 1,
having a post-treatment step for post-treating at least a portion
on which an aqueous pigment ink is printed of a textile fiber
product on which the aqueous pigment ink is printed by an inkjet
process in said printing step, by a padding process, coating
process, screen printing process, inkjet process, or spraying
process.
22. The method for inkjet textile printing according to claim 21
wherein the post-treatment is performed by applying at least one of
acrylic resin emulsion, urethane resin emulsion, crosslinking
agent, plasticizer, surfactant, and silicone-based softening agent
to at least a portion on which an aqueous pigment ink is printed of
said textile fiber product.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a method for inkjet textile
printing wherein an aqueous pigment ink is inkjet-printed on a
textile fiber product after pretreatment and a textile fiber
product prepared using the method.
[0003] 2. Description of the Prior Art
[0004] In recent years, inkjet textile printing with an ink
containing a dye or pigment as a colorant has been developed as a
method of coloring a textile fiber product with the advantage of
obviation of the need for plate making.
[0005] In the case of coloring with a dye, a textile fiber product,
pretreated with a cellulose thickener or the like in advance, is
then inkjet-printed with an ink containing a dye suitable for the
kind of fiber as a colorant. Accordingly, inks containing reactive
dyes or direct dyes for cellulose fibers such as cotton or hemp,
acid dyes for animal fibers such as wool or silk, acid dyes or
disperse dyes for nylon fibers, disperse dyes for polyester fibers,
and cationic dyes for acrylic fibers, are used as colorants
respectively. After inkjet printing, steps for steaming, washing,
soaping, drying and so on are taken to yield a textile fiber
product with desired pattern without plate making.
[0006] However, because a dye is used as a colorant, it is
necessary to change the dye (hence the ink containing the dye)
according to the kind of fiber, and problems arise from the complex
processes following inkjet printing, such as for steaming, washing,
soaping, and drying, and a tendency for increasing environmental
load.
[0007] Meanwhile, in the case of coloring with an ink containing a
pigment, which, unlike dyes, is a colorant that does not have
substantivity for fibers, there are advantages in that unlike dyes,
textile fiber products of various fibers can be colored with a
single kind of ink, and that the environmental load is low because
of the obviation of the need for steaming and washing steps after
printing, although a binder is needed to bind the pigment to the
fiber.
[0008] However, because pigments, unlike dyes, occur as insoluble
color-imparting particles, inkjet printing using a pigment ink
poses the problems of clogging in the fine nozzle of inkjet
printing machine and the possible occurrence of time-related
precipitation and flocculation of the pigment in the ink. The same
poses other problems, including a tendency for film formation on
the nozzle tip of inkjet printing machine and hence nozzle clogging
caused by the binder needed to bind the pigment to the fiber, a
tendency toward a hard feeling, and difficulty in obtaining
sufficient fastness. Still another problem can arise when a pigment
ink is printed directly on fiber: the pigment ink penetrates the
fiber, making it difficult to obtain high-density patterns, and the
pigment ink undergoes migration, making it difficult to obtain
brilliant images.
[0009] Examples of past proposals concerning color impartment by an
inkjet process using a pigment as a colorant include the techniques
described in the references (1) to (6) below.
[0010] (1) JP-A-2003-268271
[0011] A technique for performing inkjet textile printing with
excellent performance in printing stability, discharge stability,
storage stability, and washing fastness by dispersing a pigment
using an organic polymer compound having an anionic group,
previously polymerized in a solvent, thereafter distilling off the
solvent, adding an acid for acid deposition to cover the pigment
surface with the organic polymer compound, and thereafter heating a
fabric inkjet-printed using an ink prepared by blending a block
isocyanate in a colorant solubilized by the addition of water and a
base.
[0012] (2) JP-A-2009-215506
[0013] A technique for using a ink for inkjet textile printing to
print a fabric comprising a pigment, a water-dispersible resin, a
block isocyanate compound as a crosslinking agent, and water, and
exhibiting good performance in color fastness to washing and
rubbing.
[0014] (3) JP-A-2006-218791
[0015] A technique for using an inkjet recording material that
exhibits excellent performance in image brilliancy, water
resistance, light resistance, and chromogenicity, comprising a
polylactic acid fiber base and an ink receiving layer formed
thereon, the layer comprising an aqueous emulsion type acrylic
adhesive having a glass transition point ranging from -50.degree.
C. to -10.degree. C. and a water-soluble cationic polymer as
primary components.
[0016] (4) JP-A-2009-215686
[0017] A method for inkjet textile printing having both high color
fastness to rubbing and excellent chromogenicity and brilliancy,
comprising pretreating a fabric with a water dispersion of a
cationic polymer, thereafter coloring the fabric by inkjet, then
post-treating with a dispersion of a block isocyanate in water, and
heating at 120.degree. C. to 210.degree. C.
[0018] (5) JP-T-2010-503779
[0019] A method for digital printing of a fabric, comprising
(a) a step for pretreating the fabric with an aqueous pretreatment
solution containing a nonionic latex polymer and a polyvalent
cation salt solution, (b) a step for drying the pretreated fabric,
and (c) a step for digital printing the dry pretreated fabric with
a color inkjet ink, wherein the nonionic latex polymer has a
sufficient nonionic component to make it stable in the presence of
the polyvalent cation salt solution.
[0020] (6) JP-A-HEI-11-315485
[0021] A technique concerning an inkjet-printed fabric having (a)
an aqueous ink comprising an aqueous vehicle and a colorant and (b)
a fabric to be printed with the aqueous ink, wherein the fabric has
been treated with a hydrophilic composition containing at least one
kind of crosslinkable thermoplastic polymer having a molecular
weight of at least 6000, and selected from the group consisting of
(1) a polymer having at least one carboxylic acid group and at
least one crosslinkable group and (2) a polymer selected from the
group consisting of mixtures of a first polymer having at least one
carboxylic acid group and a second polymer having at least one
crosslinkable group.
[0022] However, the proposals described in the aforementioned
references (1) to (6) are problematic in the aspects shown
below.
[0023] The technique described in the reference (1) cannot be said
to be an appropriate method of obtaining a colorant because it
requires the complex steps of once finely dispersing a pigment in a
solvent system, then performing acid deposition to bind an organic
polymer compound to the pigment surface, and thereafter blending a
base to solubilize the pigment to obtain a colorant, its
workability is low, and its process is painstaking. In addition,
the pigment dispersion prepared by dispersing a pigment using such
a pigment-dispersing agent is highly viscous, and when the pigment
is dispersed to high density, the ink viscosity increases to the
extent that the ink cannot be used for inkjet; therefore, the
pigment dispersion is not considered to be suitable for an inkjet
ink of high color density. In addition, when a fabric is colored
with this ink formulated with a block isocyanate and subjected to a
heat treatment, the bindability of the ink component to the fabric
is weak, and it is unlikely that satisfactory fastness is
obtained.
[0024] In the technique described in the reference (2), like the
technique described in the reference (1), a block isocyanate
compound is formulated as a crosslinking agent in a coloring ink
only, and the crosslinking of the water-dispersible resin and block
isocyanate compound in the coloring ink alone does not cause
sufficient pigment binding to the fabric; therefore, this technique
is not considered to ensure adequate fastness.
[0025] In the technique described in the reference (3), a fiber
base is pretreated with a composition of an aqueous emulsion type
acrylic adhesive and a water-soluble cationic polymer as the
primary components in advance to cover the entire surface of the
fiber base with a resin film; therefore, it is thought that the
feeling of the fiber base hardens, and that the breathability is
adversely affected. In addition, because inkjet printing is
performed on a hydrophobic film, it is thought that brilliant
images are difficult to obtain due to ink repellency.
[0026] The technique described in the reference (4) is intended to
improve the fastness by pretreating a fabric with a cationic
polymer to increase the color development density of inkjet prints,
and post-treating the fabric with a block isocyanate compound;
however, pretreatment with the polymer hardens the feeling. In
addition, when inkjet printing is followed by a post-treatment with
a block isocyanate, crosslinking of the binder and block isocyanate
in the coloring ink occurs, improving the water resistance of the
binder; however, the binding of the fabric and the pigment and
binder is insufficient; therefore, this technique is not considered
to ensure adequate fastness for a colored fabric.
[0027] The techniques described in the references (5) and (6), like
the technique described in the reference (4), are considered to
adversely affect the feeling because of pretreatment of the fabric
with a polymer, and to make it difficult to obtain brilliant images
due to ink repellency because of inkjet printing on a hydrophobic
film.
[0028] As stated above, when using a dye as a colorant in coloring
a textile fiber product by an inkjet process, clogging in the
nozzle of inkjet apparatus is unlikely to occur, the ink discharge
stability is good, and with dyeing affinity for fiber, the quality
properties such as feeling and fastness of the colored textile
fiber product are good. In this case, however, it is necessary to
choose a dye according to the kind of fiber, and moreover, problems
arise from the complex steps that cannot be said to be efficient,
the cost requirements for equipment and resource consumption, and
the relatively high environmental load by waste liquid.
[0029] Meanwhile, when using a pigment as a colorant in coloring a
textile fiber product by an inkjet process, it is unnecessary to
choose a pigment according to the kind of fiber, and the steps are
relatively simple; however, this method poses problems concerning
the long-term storage stability of the pigment ink, possible
occurrence of clogging in the nozzle of inkjet apparatus and
discharge stability reduction, and difficulty in obtaining good
quality properties such as feeling and fastness of the colored
textile fiber product.
[0030] For this reason, there is a demand for the development of a
method of coloring a textile fiber product by an inkjet process
using an ink containing a pigment as a colorant, which method
enables the obtainment of brilliant images and a colored product
with excellent color fastness and soft feeling while preventing
clogging in the fine nozzle of inkjet printing machine.
SUMMARY OF THE INVENTION
[0031] The present invention has been developed in view of the
above-described problems in the conventional art, and is intended
to provide a method for inkjet textile printing that allows a
textile fiber product to be brilliantly colored using a pigment ink
with good quality-related properties such as feeling and color
fastness, while preventing clogging in the nozzle of inkjet
printing machine, and a textile fiber product prepared using the
same.
[0032] [1] The present inventors conducted extensive investigations
to solve the above-described problems, and have succeeded in
developing a method for inkjet textile printing that allows a
textile fiber product to be pigment-colored with soft feeling and
excellent fastness by pretreating a subject textile fiber product
with a particular cationic surfactant and block isocyanate
compound, and thereafter inkjet-printing the subject textile fiber
product with an aqueous pigment ink containing at least a
water-soluble dispersing agent having a crosslinking property, a
self-emulsifying type urethane resin, and a block isocyanate
compound.
[0033] According to this method for inkjet textile printing, by
pretreating a textile fiber product with a particular cationic
surfactant and block isocyanate compound, inkjet textile printing
of the textile fiber product with an aqueous pigment ink can be
performed brilliantly and with high density while preventing
bleeding and penetration to the maximum possible extent, and the
block isocyanate compound used in the pretreatment and/or a block
isocyanate compound in the aqueous pigment ink crosslink with the
water-soluble dispersing agent having a crosslinking property
and/or the crosslinking functional group in the self-emulsifying
type urethane resin in the aqueous pigment ink, so that the
water-soluble dispersing agent, the self-emulsifying type urethane
resin, and the block isocyanate compound become a water-insoluble
integral entity, and, while in a state containing the pigment, bind
firmly to the fiber in the textile fiber product, whereby a
pigment-colored textile fiber product with soft feeling and
excellent fastness is obtained.
[0034] [2] The method for inkjet textile printing and textile fiber
product of the present invention can be described as follows:
[0035] 1. A method for inkjet textile printing comprising a
printing step for printing an aqueous pigment ink on a specifically
pretreated portion of a textile fiber product by an inkjet
process,
wherein said specific pretreatment is performed by applying at
least: (A) a quaternary ammonium salt type cationic surfactant
represented by the formula (1) below, and (B) a block isocyanate
compound to the entire textile fiber product or a required portion
thereof, and said aqueous pigment ink comprises at least a pigment,
an aqueous liquid as a solvent or dispersion medium, and: (C) a
water-soluble dispersing agent having a crosslinking property, (D)
a self-emulsifying type urethane resin, and (E) a block isocyanate
compound.
##STR00002##
[In the formula (1), two of R.sup.1 to R.sup.4 mutually
independently represent an alkyl group having 8 to 18 carbon atoms,
the remaining two mutually independently represent a methyl group
or an ethyl group, and X.sup.- represents an anion.]
[0036] 2. The method for inkjet textile printing in 1 above, having
a pretreatment step for performing the specific pretreatment on the
entire textile fiber product or a required portion thereof prior to
said printing step.
[0037] 3. The method for inkjet textile printing in 1 or 2 above
wherein the pretreatment is performed by applying a pretreatment
agent containing at least:
(A) a cationic surfactant represented by the formula (1) and (B) a
block isocyanate compound to the entire textile fiber product or a
required portion thereof.
[0038] 4. The method for inkjet textile printing in 1, 2 or 3 above
wherein (B) the block isocyanate compound is a compound resulting
from blocking of the isocyanate group in
trimethylolpropane adduct form or isocyanurate form of:
hexamethylene diisocyanate, hydrogenated xylylene diisocyanate,
isophorone diisocyanate, or dicyclohexylmethane diisocyanate.
[0039] 5. The method for inkjet textile printing in 4 above wherein
(B) the block isocyanate compound has been obtained using diethyl
malonate, diisopropylamine, 1,2,4-triazole, 3,5-dimethylpyrazole,
or 2-butanonoxime as a blocking agent.
[0040] 6. The method for inkjet textile printing in any one of 1 to
5 above wherein the aqueous pigment ink is a dispersion liquid
containing a dispersed pigment having a maximum particle diameter
of not more than 500 nm.
[0041] 7. The method for inkjet textile printing in any one of 1 to
6 above wherein (C) the water-soluble dispersing agent having a
crosslinking property results from neutralization, with a basic
substance, of an emulsion polymer having a molecular weight of
2,000 to 20,000 obtained from:
(1) 20 to 80 parts by weight of a (meth)acrylic acid ester monomer
represented by CH.sub.2.dbd.CR.sup.5--COOR.sup.6 [wherein R.sup.5
represents a hydrogen atom or a methyl group, and R.sup.6
represents an alkyl group having 2 to 8 carbon atoms.], (2) 80 to
20 parts of an aliphatic vinyl monomer having a carboxyl group, and
(3) 0 to 20 parts of an aliphatic vinyl monomer having a
crosslinking property.
[0042] 8. The method for inkjet textile printing in 7 above wherein
(2) the aliphatic vinyl monomer having a carboxyl group is at least
one selected from the group consisting of acrylic acid, methacrylic
acid, itaconic acid, maleic acid, and fumaric acid.
[0043] 9. The method for inkjet textile printing in 7 or 8 above
wherein the basic substance is a secondary amine or a tertiary
amine.
[0044] 10. The method for inkjet textile printing in any one of 1
to 9 above wherein the blending ratio of (C) the water-soluble
dispersing agent having a crosslinking property in the aqueous
pigment ink ranges from 0.05 to 2.0 parts by weight relative to 1.0
part by weight of the pigment.
[0045] 11. The method for inkjet textile printing in any one of 1
to 10 above wherein the aqueous pigment ink contains a
polyoxyethylene styrenated phenyl ether sulfate or a
polyoxyethylene alkyl ether sulfate as a dispersing aid.
[0046] 12. The method for inkjet textile printing in any one of 1
to 11 above wherein (D) the self-emulsifying type urethane resin
has been obtained from a composition comprising at least:
an isocyanate and a polyol having a carboxyl group or a sulfonic
acid group.
[0047] 13. The method for inkjet textile printing in any one of 1
to 12 above wherein the glass transition point (Tg) of (D) the
self-emulsifying type urethane resin is -60 to 20.degree. C.
[0048] 14. The method for inkjet textile printing in any one of 1
to 13 above wherein (E) the block isocyanate compound is a compound
resulting from blocking the isocyanate group in
trimethylolpropane adduct form or isocyanurate form of:
hexamethylene diisocyanate, hydrogenated xylylene diisocyanate,
isophorone diisocyanate, or dicyclohexylmethane diisocyanate.
[0049] 15. The method for inkjet textile printing in 14 above
wherein (E) the block isocyanate compound has been obtained with
diethyl malonate, diisopropylamine, 1,2,4-triazole,
3,5-dimethylpyrazole, or 2-butanonoxime as a blocking agent.
[0050] 16. The method for inkjet textile printing in any one of 1
to 15 above wherein (E) the block isocyanate compound is
water-soluble or self-emulsifying, and wherein the aqueous pigment
ink is excellently redispersible.
[0051] 17. The method for inkjet textile printing in any one of 1
to 16 above wherein the viscosity of the aqueous pigment ink is 3
to 30 mPas at 20.degree. C.
[0052] 18. The method for inkjet textile printing in any one of 1
to 17 above wherein the surface tension of the aqueous pigment ink
is 20 to 40 mN/m.
[0053] 19. The method for inkjet textile printing in any one of 1
to 18 above, having a heat treatment step for heating at least a
portion on which an aqueous pigment ink is printed of a textile
fiber product on which the aqueous pigment ink is printed by an
inkjet process in said printing step.
[0054] 20. The method for inkjet textile printing in any one of 1
to 19 above wherein the pretreatment is performed by applying at
least:
(A) a cationic surfactant represented by the formula (1) above and
(B) a block isocyanate compound to the entire textile fiber product
or a required portion thereof by a padding process, coating
process, screen printing process, inkjet process, or spraying
process.
[0055] 21. The method for inkjet textile printing in any one of 1
to 20 above, having a post-treatment step for post-treating at
least a portion on which an aqueous pigment ink is printed of a
textile fiber product on which the aqueous pigment ink is printed
by an inkjet process in said printing step, by a padding process,
coating process, screen printing process, inkjet process, or
spraying process.
[0056] 22. The method for inkjet textile printing in 21 above
wherein the post-treatment is performed by applying at least one of
acrylic resin emulsion, urethane resin emulsion, crosslinking
agent, plasticizer, surfactant, and silicone-based softening agent
to at least a portion on which an aqueous pigment ink is printed of
said textile fiber product.
[0057] 23. A textile fiber product printed by the method for inkjet
textile printing in any one of 1 to 22 above.
[0058] [3] The present invention has been developed on the basis of
the findings shown below.
(1) Problems in Inkjet Textile Printing Using a Pigment Ink
[0059] Inkjet textile printing using an ink with a pigment as a
colorant is exemplified by:
a method comprising blending water, a hydrophilic solvent such as a
wetting agent, an emulsion type resin as a binder, and the like
with pigment using a nonionic surfactant or an anionic surfactant
as a pigment-dispersing agent to obtain an ink, and thereafter
textile printing a desired pattern on a textile fiber product with
the ink; a method comprising printing on a cloth pretreated with a
cationic polymer and an acrylic emulsion resin (adhesive) in
advance; a method comprising dispersing a pigment using an organic
polymer compound having an anionic group, previously polymerized in
a solvent, then distilling off the solvent, thereafter adding an
acid for acid deposition to cover the pigment surface with the
organic polymer compound, thereafter adding water and a base to
obtain a solubilized microcapsulated pigment, blending a block
isocyanate in this covered pigment to obtain an ink, printing the
ink by an inkjet process, and performing a heat treatment; a method
comprising dispersing a pigment using a water-dispersible resin,
adding a block isocyanate as a crosslinking agent, and performing a
heat treatment, to achieve coloring with excellent fastness; and
the like; however, these methods have the problems shown below.
[0060] (1-1) When using a nonionic surfactant or an anionic
surfactant as a pigment-dispersing agent, a pigment dispersion that
possesses excellent long-term stability and is suitable for inkjet
can be obtained because of their high dispersion capacity. However,
when used to color a textile fiber product, this tends to inhibit
pigment binding due to poor fiber affinity. In addition, the
surfactant remaining on the textile fiber product has adverse
effects on the color fastness to washing and rubbing and the like
of the textile fiber product due to the water solubility
thereof.
[0061] (1-2) For a microcapsulated pigment prepared by dispersing a
pigment using an organic polymer compound having an anionic group,
subjecting it to acid deposition, and redissolving it using a base,
the water resistance can be improved by covering the pigment
surface with the organic polymer; however, the productivity is poor
because extremely complex production steps are required. In
addition, because acid deposition and redissolution with a base are
required after dispersion, some portion of the pigment flocculates,
tending to cause color density reduction, precipitation and
increased viscosity, nozzle clogging, and the like during long-time
storage. In addition, a pigment dispersion prepared using a
water-dispersible resin that also serves as a binder is dispersible
in water and hence highly oleophilic, resulting in increased
viscosity at the time of pigment dispersion. In addition, when the
solvent water volatilizes, the pigment becomes insoluble in water
and is likely to cause clogging at the nozzle tip.
[0062] (1-3) In the method wherein a cationic polymer and an
acrylic emulsion resin are previously applied to the surface of a
textile fiber product to bind a pigment to the textile fiber
product, and the surface is inkjet-printed to bind the pigment to
the textile fiber product, sufficient fastness cannot be retained
because the bound pigment binds to the surface only ionically. In
addition, while the cationic polymer is used in combination with an
acrylic resin (adhesive), inkjet printing is performed on a dry
resin film, so that the pigment adheres to the resin surface, and
the degree of fastness is insufficient. In addition, because a
pretreatment agent is applied over the entire textile fiber
product, the feeling and touch worsen, and the breathability tends
to be adversely affected. On the other hand, to bind the pigment to
the textile fiber product surface without pretreatment, it is
necessary to blend a large amount of an emulsion resin for binding
in the ink. Although the emulsion resin for binding is capable of
firmly bonding the pigment to the textile fiber product, it forms a
water-insoluble film upon drying; therefore, large-amount blending
thereof can cause inkjet nozzle clogging and hardens the feeling of
the colored portion in the textile fiber product.
[0063] (1-4) Although the occurrence of inkjet nozzle clogging due
to large-amount blending of an emulsion resin in (1-3) above may be
prevented by blending a large amount of wetting agent to delay the
drying, blending of a large amount of wetting agent can
significantly reduce the fastness of the colored portion in the
textile fiber product, and even when a wetting agent is blended in
a large amount, nozzle tip clogging cannot be prevented
completely.
[0064] (1-5) In the method wherein a block isocyanate and water are
added to a pigment covered with an organic polymer compound having
a carboxyl group, inkjet printing is performed, and thereafter
heating is performed to color a textile fiber product, the pigment
can be water-insolubilized on the textile fiber product surface
through the reaction of the carboxyl group and the isocyanate
group; however, as stated above, the covered pigment in an inkjet
ink tends to deteriorate the long-term storage stability of the
inkjet ink due to the complex production steps. In addition,
through the reaction of the carboxyl group and the isocyanate group
only, it is difficult to obtain sufficient color fastness (fastness
to washing, fastness to rubbing, and the like) at the colored
portion in the textile fiber product.
(2) Solutions to the Problems
[0065] (2-1) By applying a particular cationic surfactant to a
textile fiber product in a pretreatment, an ion complex is formed
with an aqueous pigment ink to prevent bleeding and penetration to
the maximum possible extent, thus enabling brilliant printing with
high density. Because no resin is used in the pretreatment, the
feeling of the textile fiber product is not adversely affected.
[0066] (2-2) Use of a cationic surfactant in (2-1) above is feared
to reduce fastness properties such as water resistance; however, by
using a block isocyanate compound in the pretreatment above, and
also using a water-soluble dispersing agent having a crosslinking
property and a self-emulsifying type urethane resin in the aqueous
pigment ink, the block isocyanate compound in the pretreatment and
the water-soluble dispersing agent having a crosslinking property
and/or the crosslinking functional group in the self-emulsifying
type urethane resin in the aqueous pigment ink crosslink with each
other, making the pigment, the water-soluble dispersing agent
having a crosslinking property, the self-emulsifying type urethane
resin, and the block isocyanate compound an integral entity, and
ensuring sufficient fastness.
[0067] (2-3) By blending a pigment dispersion obtained using a
water-soluble dispersing agent having a crosslinking property, a
self-emulsifying type urethane resin as a binder, and a block
isocyanate compound as a crosslinking agent, an aqueous pigment ink
for inkjet that is of low viscosity and high color density and
possesses excellent printing workability and long-term storage
stability, is obtained. Furthermore, the block isocyanate compound
in the pretreatment and/or the block isocyanate compound in the
aqueous pigment ink and the water-soluble dispersing agent having a
crosslinking property and/or the crosslinking functional group in
the self-emulsifying type urethane resin in the aqueous pigment ink
crosslink with each other, whereby they become water-insoluble and
function as a pigment binder; therefore, a textile fiber product
possessing good fastness in the colored portion is obtained while
preventing the feeling from being adversely affected.
[0068] (3) According to the method for inkjet textile printing of
the present invention, which is based on the above-described
aspects, in addition to the advantages of conventional inkjet
textile printing arising from the possibility of textile printing
without plate making, i.e., small lot size, multiple varieties,
quick delivery, no requirement of plate making cost, and
possibility of extremely efficient textile printing, inkjet
printing of a textile fiber product with an aqueous pigment ink can
be performed brilliantly with high density while preventing
bleeding and penetration to the maximum possible extent by
pretreating a textile fiber product with a particular cationic
surfactant and block isocyanate compound, and the block isocyanate
compound used in the pretreatment and/or the block isocyanate
compound in the aqueous pigment ink and the water-soluble
dispersing agent having a crosslinking property and/or the
crosslinking functional group in the self-emulsifying type urethane
resin in the aqueous pigment ink crosslink with each other, whereby
the water-soluble dispersing agent, the self-emulsifying type
urethane resin, and the block isocyanate compound become a
water-insoluble integral entity, and, while in a state containing
the pigment, bind firmly to the fiber in the textile fiber product,
whereby a pigment-colored textile fiber product with soft feeling
and excellent fastness is obtained.
[0069] In the method for inkjet textile printing of the present
invention, an ion complex is formed by a particular cationic
surfactant and an aqueous pigment ink in a pretreatment, and the
block isocyanate compound in the pretreatment and/or the block
isocyanate compound in an aqueous pigment ink and the water-soluble
dispersing agent having a crosslinking property and/or the
crosslinking functional group in the self-emulsifying type urethane
resin in the aqueous pigment ink crosslink with each other, or
moreover the block isocyanate compound itself condenses, a desired
effect is obtained; if any constituent is lacking, the object of
the present invention cannot be accomplished. Accordingly, the
configuration of the present invention is of particular
significance.
[0070] According to the present invention, by pretreating a textile
fiber product with a particular cationic surfactant and block
isocyanate compound, inkjet printing of an aqueous pigment ink on
the textile fiber product can be performed brilliantly with high
density while preventing bleeding and penetration to the maximum
possible extent, and the block isocyanate compound used in the
pretreatment and/or the block isocyanate compound in the aqueous
pigment ink and the water-soluble dispersing agent having a
crosslinking property and/or the crosslinking functional group in
the self-emulsifying type urethane resin in the aqueous pigment ink
crosslink with each other, whereby the water-soluble dispersing
agent, the self-emulsifying type urethane resin, and the block
isocyanate compound become a water-insoluble integral entity, and,
while in a state containing the pigment, bind firmly to the fiber
in the textile fiber product, whereby a pigment-colored textile
fiber product with soft feeling and excellent fastness is
obtained.
DETAILED DESCRIPTION OF THE INVENTION
[0071] Modes for embodying the present invention are described
below.
[0072] (1) Textile Fiber Product
[0073] textile fiber products that can serve as the subject for the
method for inkjet textile printing of the present invention include
fabrics, knits, non-woven fabrics, gigged cloths, and the like
configured with various fibers, whether in the form of material
cloths, garments (shirts, sweatshirts, jerseys, pants, one-piece
dresses, blouses, hats and caps, socks, and the like), apparel
accessories (handkerchiefs, neckties, cloth belts, and the like),
or other products (shoes, beddings, bed sheets, curtains, car
seats, bags, flags, and the like). Even those having a portion
configured with a non-fiber component are, as a rule, not excluded
from the scope of the subject.
[0074] The fiber that constitutes the textile fiber product, as a
rule, is also subject to no limitation; for example, the subject
may be a textile fiber product configured by any one of various
synthetic fibers, semi-synthetic fibers, natural fibers, and
inorganic fibers (including mixed-spun fabrics thereof) such as
nylon, polyester, acryl, lactate fiber, acetate, rayon, cotton,
silk, wool, hemp, and glass fiber.
Not only for white fiber products, but also for chromatic fiber
products, a desired pattern and the like including a color image
can be formed by, for example, textile printing with a white
masking aqueous pigment ink using the method for inkjet textile
printing of the present invention, and thereafter textile printing
with a chromatic aqueous pigment ink using the method for inkjet
textile printing of the present invention.
[0075] (2) Pretreatment
[0076] The method for inkjet textile printing of the present
invention encompasses not only methods comprising a pretreatment
step for a textile fiber product, but also cases where a
pretreatment has previously been performed on the textile fiber
product.
[0077] The pretreatment in the present invention is performed by
applying at least:
(A) a quaternary ammonium salt type cationic surfactant represented
by the formula (1) above and (B) a block isocyanate compound to the
entire textile fiber product or a required portion thereof.
[0078] In this pretreatment, a cationic surfactant of the formula
(1) and a block isocyanate compound may be separately applied to a
textile fiber product (e.g., impregnated in, or bonded to, the
textile fiber product), and a single pretreatment agent containing
both may also be applied to a textile fiber product.
[0079] (a) Quaternary Ammonium Salt Type Cationic Surfactant
Represented by Formula (1)
[0080] By applying a quaternary ammonium salt type cationic
surfactant of the formula (1) to the entire textile fiber product
or a desired portion thereof in the pretreatment, an ion complex is
formed with the aqueous pigment ink that is to be subsequently
inkjet-printed. For this reason, without causing color fastness
reduction, the bleeding and penetration of aqueous pigment ink is
prevented to the maximum possible extent, enabling brilliant inkjet
printing with high color density using the aqueous pigment ink.
[0081] In the pretreatment, a quaternary ammonium salt type
cationic surfactant of the formula (1) can be applied to a textile
fiber product in an amount that prevents the bleeding and
penetration of the aqueous pigment ink. If the amount applied is
large, fastness properties such as water resistance can decrease,
and if the amount applied is small, the prevention of bleeding and
penetration can become insufficient.
[0082] Any two of R.sup.1 to R.sup.4 in the formula (1) should be
mutually independently alkyl groups having 8 to 18 carbon atoms,
and the other two should be mutually independently a methyl group
or an ethyl group.
[0083] When two of the aforementioned four alkyl groups is a methyl
group or an ethyl group, the quaternary ammonium salt type cationic
surfactant of the formula (1) becomes water-soluble, and, when
constituting a pretreatment agent along with a block isocyanate
compound, makes the storage stability of the pretreatment agent
good.
[0084] If the carbon number of one or both of the other two alkyl
groups in the aforementioned four alkyl groups is less than 8, the
water resistance decreases. Meanwhile, if the carbon number of one
or both of the two alkyl groups is more than 18, brilliant inkjet
textile printing of an aqueous pigment ink with high color density
becomes difficult to perform, and, when the quaternary ammonium
salt type cationic surfactant of the formula (1) constitutes a
pretreatment agent along with a block isocyanate compound, the
storage stability of the pretreatment agent decreases due to
increased likelihood of phase separation and the like.
[0085] The alkyl group having 8 to 18 carbon atoms in the formula
(1) may be linear or branched; examples include, but are not
limited to, octyl group, nonyl group, decyl group, dodecyl group,
tetradecyl group, octadecyl group, isooctyl group,
2,4-dimethylhexyl group, 4-ethyl-2-methylheptyl group, and the
like.
[0086] For the quaternary ammonium salt type cationic surfactant of
the formula (1), when all of the four alkyl groups are methyl
groups or ethyl groups, the hydrophilicity increases, but the
fastness of the colors imparted by the aqueous pigment ink
decreases. Meanwhile, when all of the four alkyl groups have a
carbon number of 8 to 18, the hydrophobicity of the surfactant of
the formula (1) increases, so that the water resistance improves,
but water-solubility is not achieved. Furthermore, if only one
alkyl group has 8 to 18 carbon atoms, the water resistance of the
surfactant of the formula (1) is insufficient; when two alkyl
groups have 8 to 18 carbon atoms and the other two alkyl groups are
methyl group(s) or ethyl group(s) in a ratio of 1:1 of both, an
appropriate balance is obtained between the water solubility and
the color fastness.
[0087] X.sup.- in the formula (1) represents an anion. Examples of
the anion include halide ion, inorganic acid ion, organic acid ion,
and hydroxide ion. More specific examples of halide ion, inorganic
acid ion, and organic acid ion include, but are not limited to,
chloride ion, bromide ion, sulfate ion, nitrate ion, phosphate ion,
acetate ion, malonate ion, and the like.
[0088] (B) Block Isocyanate Compound
[0089] As the block isocyanate compound used in the pretreatment in
the present invention, one having a group that is reactive with (C)
a water-soluble dispersing agent having a crosslinking property and
(D) a crosslinking functional group in a self-emulsifying type
urethane resin upon heating (preferably heating at 100.degree. C.
or higher) (e.g., one having 2 or 3 or more such groups) can be
used.
[0090] When applying the block isocyanate compound in the present
invention to a textile fiber product in pretreatment, the compound
crosslinks with the water-soluble dispersing agent having a
crosslinking property and self-emulsifying type urethane resin in
the aqueous pigment ink that is to be used for inkjet printing, and
they become water-insoluble and bind to the textile fiber product.
In addition, the block isocyanate compound itself condenses and
binds to the textile fiber product, thus capable of exhibiting a
primer-like function.
[0091] In the pretreatment, the block isocyanate compound is
preferably applied to the textile fiber product in an amount at
least larger than the amount that just fits the reacting
water-soluble dispersing agent having a crosslinking property and
the number of crosslinking functional groups in the
self-emulsifying type urethane resin. If the amount applied is too
large, the feeling of the textile fiber product can harden, and if
the amount applied is small, the color fastness can decrease.
[0092] The block isocyanate compound is preferably a compound
resulting from blocking the isocyanate group in:
TMP (trimethylolpropane) adduct form or isocyanurate form of: HDI
(hexamethylene diisocyanate), H6XDI (hydrogenated xylylene
diisocyanate), IPDI (isophorone diisocyanate), or H12MDI
(dicyclohexylmethane diisocyanate). In this case, the blocking
agent is preferably DEM (diethyl malonate), DIPA
(diisopropylamine), TRIA (1,2,4-triazole), DMP
(3,5-dimethylpyrazole), or MEKO (2-butanonoxime), which, however,
are not to be construed as limiting.
[0093] The block isocyanate compound (B) in the present invention
can be used as an oligomer resulting from reacting some of the
isocyanate groups thereof with polyol, polycarbonate, polyester, or
polyether, or the like.
[0094] (3) Pretreatment Agent
[0095] The pretreatment agent used to pretreat a textile fiber
product in the present invention contains at least:
(A) a quaternary ammonium salt type cationic surfactant represented
by the formula (1) and (B) a block isocyanate compound.
[0096] In addition to the above-described components, the
pretreatment agent may be blended as appropriate with water, a
water-soluble organic solvent, an antioxidant, a drying inhibitor,
an ultraviolet absorbent, a crosslinking catalyst, a plasticizer, a
defoaming agent, and the like.
[0097] In the pretreatment agent, the amount blended of the
quaternary ammonium salt type cationic surfactant represented by
the formula (1) can be, for example, 0.5 to 20% by weight, and the
amount blended of the block isocyanate compound can be, for
example, 0.5 to 15% by weight.
[0098] The amount blended of the quaternary ammonium salt type
cationic surfactant of the formula (1) in the pretreatment agent
need to be an amount that prevents the bleeding and penetration of
the aqueous pigment ink, and is preferably not more than 20 parts,
more preferably not more than 10 parts, still more preferably not
more than 5 parts, relative to 100 parts of the pretreatment agent.
If the amount blended is large, color fastness properties such as
water resistance decrease, and if the amount blended is small, it
is feared that the bleeding and penetration of the aqueous pigment
ink cannot be prevented.
[0099] It is desirable that the amount blended of the block
isocyanate compound in the pretreatment agent be an amount larger
than the amount that just fits the reacting water-soluble
dispersing agent having a crosslinking property and the number of
crosslinking functional groups in the self-emulsifying type
urethane resin. The amount blended of the block isocyanate compound
relative to 100 parts of the pretreatment agent is preferably not
more than 15 parts, more preferably not more than 10 parts, still
more preferably not more than 5 parts. If the amount blended is
larger than these levels, the feeling of the textile fiber product
can harden, and if the amount blended is smaller, the color
fastness can decrease.
[0100] (4) Method of Pretreatment
[0101] The pretreatment in the present invention can be performed
by applying a cationic surfactant represented by the formula (1)
and a block isocyanate compound (or a pretreatment agent containing
at least them) to the entire textile fiber product or a required
portion thereof by padding process, coating process, screen
printing process, inkjet process, or spraying process.
[0102] After thus applying a pretreatment agent and the like to a
textile fiber product, the textile fiber product can be
inkjet-printed with an aqueous pigment ink in a wet state, or after
being dried, or after being subjected to a heat treatment.
[0103] (5) Printing Step
[0104] In the method for inkjet textile printing of the present
invention, a portion that has been subjected to the aforementioned
pretreatment of a textile fiber product is printed with an aqueous
pigment ink by an inkjet process.
[0105] All of the desired portions in the subject textile fiber
product may be subjected to a printing step after completing the
pretreatment step for all of the desired portions; in addition, for
example, some desired portions in the subject textile fiber product
may be sequentially subjected to a pretreatment step, and before
completing the pretreatment step for all of the desired portions,
the portions for which the pretreatment step has been completed may
be sequentially subjected to a printing step.
[0106] (6) Aqueous Pigment Ink
[0107] In the present invention, the aqueous pigment ink comprises
at least a pigment, an aqueous liquid as a solvent or dispersion
medium, and:
(C) a water-soluble dispersing agent having a crosslinking
property, (D) a self-emulsifying type urethane resin, and (E) a
block isocyanate compound.
[0108] (C) Water-Soluble Dispersing Agent Having a Crosslinking
Property
[0109] The water-soluble dispersing agent having a crosslinking
property in the present invention and (D) a self-emulsifying type
urethane resin crosslink with (B) the block isocyanate compound in
the pretreatment and/or (E) the block isocyanate compound in the
aqueous pigment ink, whereby they become a water-insoluble integral
entity, and, while in a state containing the pigment, bind firmly
to the fiber in the textile fiber product.
[0110] The water-soluble dispersing agent having a crosslinking
property in the present invention is exemplified by one prepared by
neutralizing:
(C4) an emulsion polymer consisting of: (C1) a (meth)acrylic acid
ester monomer, (C2) an aliphatic vinyl monomer having a carboxyl
group, and (C3) an aliphatic vinyl monomer having a crosslinking
property with (C5) a basic substance.
[0111] In the present invention, the blending ratio of the
water-soluble dispersing agent having a crosslinking property in
the aqueous pigment ink preferably ranges from 0.05 to 2.0 parts by
weight relative to 1.0 part by weight of the pigment; if the
blending ratio is lower than 0.05, the dispersion viscosity can
increase, and if the blending ratio is higher than 2.0, the
time-related viscosity stability can decrease.
[0112] (C1) (Meth)Acrylic Acid Ester Monomer
[0113] As the (meth)acrylic acid ester monomer, one represented by
CH.sub.2.dbd.CR.sup.5--COOR.sup.6 [wherein R.sup.5 represents a
hydrogen atom or a methyl group, and R.sup.6 represents an alkyl
group having 2 to 8 carbon atoms.] can be used suitably.
[0114] When R.sup.6 is a hydrogen atom or an alkyl group having 1
carbon atom, the colored portion of the textile fiber product lacks
water resistance or becomes insufficiently resistant to water; when
R.sup.6 is an alkyl group having not less than 9 carbon atoms, the
pigment dispersibility worsens; when R.sup.6 has an aromatic ring,
the viscosity of the aqueous pigment ink increases, and the
time-related viscosity stability worsens.
[0115] Examples of this (meth)acrylic acid ester monomer include
ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate,
pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate,
2-ethylhexyl (meth)acrylate, and the like. In the present
invention, such (meth)acrylic acid ester monomers may be used alone
or in combination of two kinds or more.
[0116] (C2) Aliphatic Vinyl Monomer Having a Carboxyl Group
[0117] Examples of the aliphatic vinyl monomer having a carboxyl
group include acrylic acid, methacrylic acid, itaconic acid, maleic
acid, fumaric acid, and the like. In the present invention, such
aliphatic vinyl monomers having a carboxyl group may be used alone
or in combination of two kinds or more.
[0118] (C3) Aliphatic Vinyl Monomer Having a Crosslinking
Property
[0119] As the aliphatic vinyl monomer having a crosslinking
property, an aliphatic vinyl monomer having a crosslinking
functional group other than a carboxyl group that is
copolymerizable with the aforementioned (meth)acrylic acid ester
monomer can be used. Examples include, but are not limited to,
(meth)hydroxy acrylate, (meth)acrylonitrile, acrylamide, vinyl
monomers containing a urethane group with a hydroxyl group, epoxy
group-containing vinyl monomers, ester group-containing vinyl
monomers formed from a monomer of a higher carboxylic acid and
polyalcohol or the like, silicone group-containing vinyl monomers
that form an organosiloxane and the like, vinylsulfonic acid,
2-acrylamide-2-methylpropanesulfonic acid, sulfuric acid esters of
2-hydroxyalkyl (meth)acrylate, vinylphosphonic acid, phosphoric
acid esters of hydroxyalkyl(meth)acrylate, (meth)acrylate
alkylphosphonic acid, vinyl alcohol, N-ethylmethacrylamide,
N-isopropylacrylamide, N-vinylpyrrolidone, and the like.
[0120] (C4) Emulsion Polymer
[0121] The monomer can be polymerized by, for example, vinyl
polymerization using an ordinary method of emulsification
polymerization. For example, a desired emulsion polymer is obtained
by carrying out a reaction in the presence of a polymerization
catalyst, (C4-a) an emulsifying dispersing agent, and (C4-b) a
chain transfer agent at 50 to 90.degree. C. for about 4 to 10
hours.
[0122] The ratio of (C1) (meth)acrylic acid ester monomer that is
suitable for the present invention ranges from 20 to 80 parts, more
preferably from 30 to 70 parts, relative to 100 parts of the total
monomer content, and from the viewpoint of the fastness of the
colored portion, the ratio still more preferably ranges from 40 to
60 parts. If the ratio is less than 20 parts, water resistance is
difficult to obtain after crosslinking, and if the ratio exceeds 80
parts, the emulsion polymer is unlikely to become water-soluble
even when neutralized with a basic substance.
[0123] From the viewpoint of viscosity reduction at the time of
pigment dispersion and time-related viscosity stability, the ratio
of (C2) aliphatic vinyl monomer having a carboxyl group that is
suitable for the present invention is 80 to 20 parts relative to
100 parts of the total monomer content. Preferably, the ratio
ranges from 70 to 30 parts, still more preferably from 60 to 40
parts. If the ratio exceeds 80 parts, water resistance is difficult
to obtain in the colored portion after crosslinking, and if the
ratio is less than 20 parts, the emulsion polymer is unlikely to
become water-soluble.
The ratio of (C3) aliphatic vinyl monomer having a crosslinking
property that is suitable for the present invention is 0 to 20
parts, more preferably 0 to 15 parts, relative to 100 parts of the
total monomer content. If the ratio exceeds 20 parts, the pigment
dispersibility decreases, and, depending on the kind of monomer,
the emulsion polymer cannot become water-soluble.
[0124] The molecular weight obtained after polymerization may be,
for example, 2,000 to 20,000, preferably ranges from 3,000 to
10,000. If the molecular weight exceeds 20,000, the dispersion
viscosity is likely to be high, and the pigment dispersibility can
decrease. If the molecular weight is less than 2,000, the
bindability of the pigment can be insufficient.
[0125] (C4-a) Emulsifying Dispersing Agent
[0126] As the emulsifying dispersing agent, a nonionic or anionic
surfactant, for example, can be used. In particular, the water
resistance of the colored portion improves when using a reactive
surfactant that is copolymerizable with the monomer at the time of
polymerization.
[0127] Examples of the reactive surfactant include, but are not
limited to, polyoxyethylene alkenyl ether ammonium sulfate,
polyoxyethylene nonylpropenylphenyl ether, polyoxyalkylene alkenyl
ether ammonium sulfate, polyoxyalkylene alkenyl ether, and the
like. These surfactants may be used alone or in combination of two
kinds or more.
[0128] (C4-b) Chain Transfer Agent
[0129] The chain transfer agent is intended to adjust the emulsion
polymer to a desired molecular weight of 2,000 to 20,000; examples
include mercapto compounds, carbon tetrachloride,
alpha-methylstyrene dimers, and the like, and use of a
mercapto-based chain transfer agent such as n-octylmercaptan,
n-dodecylmercaptan, 3-mercapto propionate, 3,3'-thiodipropionic
acid, or thioglycolic acid is suitable in controlling the molecular
weight.
[0130] The amount blended of the chain transfer agent preferably
ranges from 0.02 to 0.1 (ratio by weight), still more preferably
from 0.04 to 0.08, relative to 1.0 of the total monomer
content.
[0131] (C5) Basic Substance
[0132] The basic substance is used as a neutralizing agent for the
emulsion polymer, and may be any basic substance. For example,
ammonia, basic metal salts, primary amine compounds, secondary
amine compounds, tertiary amine compounds, and the like can be
used. Above all, in view of increasing the resolubility of the
pigment dispersion, it is preferable that neutralization be
performed with a secondary or tertiary amine compound. The emulsion
polymer is neutralized to a pH of 6 to 9 with these basic compounds
to yield a water-soluble dispersing agent having a crosslinking
property.
[0133] Neutralizing agents include, but are not limited to,
isopropylamine, t-butylamine, n-propylamine,
N,N-dimethylethanolamine, diethylethanolamine, diethanolamine,
triethylamine, triethanolamine, and the like. These may be used
alone or in combination of two kinds or more.
[0134] (D) Self-Emulsifying Type Urethane Resin
[0135] The self-emulsifying type urethane resin in the present
invention and (C) a water-soluble dispersing agent having a
crosslinking property crosslink with (B) the block isocyanate
compound in the pretreatment and/or (E) the block isocyanate
compound in the aqueous pigment ink, whereby they become a
water-insoluble integral entity, and, while in a state containing
the pigment, bind firmly to the fiber in the textile fiber product
and pigment-color the textile fiber product.
[0136] Generally, urethane resins are roughly divided into the
water-soluble type, the self-emulsifying type, and the forcibly
emulsified type.
[0137] A water-soluble type urethane resin has been polymerized
using a hydrophilic polyol; because the resin itself is
water-soluble, it is difficult to obtain desired water resistance
for the colored portion when the resin is blended in the aqueous
pigment ink. A forcibly emulsified type urethane resin has been
polymerized in the presence of a surfactant; the resin itself is
hydrophobic, the particle diameter is large, film formation is
likely to occur when the resin is blended in the aqueous pigment
ink, defective pixels and print irregularity are likely to occur
due to head nozzle tip clogging when continuous printing is
performed, and the long-term storage stability of the aqueous
pigment ink is low.
[0138] Meanwhile, a self-emulsifying type urethane resin has been
prepared by conferring a hydrophilic group to one end of urethane
resin, and emulsifying the urethane resin in water by the action of
the hydrophilic group. When blended in an aqueous pigment ink, a
self-emulsifying type urethane resin has a fine particle diameter,
is unlikely to form a film, is suitable for continuous printing,
and possesses excellent long-term storage stability. In addition, a
self-emulsifying type urethane resin becomes hydrophobic when
crosslinking the terminal hydrophilic group thereof with a block
isocyanate compound, and, along with the crosslinked form of (C) a
water-soluble dispersing agent having a crosslinking property,
becomes a pigment binder with excellent fastness.
[0139] As the self-emulsifying type urethane resin in the present
invention, for example, a self-emulsifying type urethane resin
prepared by dispersing in water a urethane prepolymer consisting at
least of a polyol, an isocyanate, an anionic group-incorporating
polyol wherein said anionic group is selected from a carboxyl group
and/or a sulfonic acid group using an anionic group-neutralizing
agent to elongate the chain can be used.
[0140] The aforementioned polyol component is not particularly
limited; for example, polyether polyols, polyester polyols,
polyester polycarbonate polyols, and the like can be used.
[0141] More specifically, examples include low-molecular-weight
polyols such as ethylene glycol, diethylene glycol, 1,2-propylene
glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene
glycol, 1,4-butylene glycol, hexamethylene glycol, and ethylene
oxide and/or propylene oxide addition products of hydrogenated
bisphenol A; polyethylene glycol; polypropylene glycol;
polytetramethylene glycol; polyether polyols prepared by adding
ethylene oxide and/or propylene oxide with such a
low-molecular-weight polyol as an initiator; polyester polyols
prepared by an esterification reaction of such a
low-molecular-weight polyol and a polyvalent carboxylic acid such
as oxalic acid, malonic acid, succinic acid, or adipic acid, or an
ester, acid anhydride or the like thereof; reaction products of a
polyester glycol and an alkylene carbonate such as polycaprolactone
polyol; polyester polycarbonate polyols that are reaction products
prepared by reacting an organic dicarboxylic acid with a reaction
product of ethylene carbonate and a polyhydric alcohol.
[0142] The isocyanate is not particularly limited; diisocyanates,
polyisocyanates having three or more isocyanate groups in the
molecular structure thereof, and the like can be used.
[0143] Examples of diisocyanates include aromatic diisocyanates
such as tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate,
p-phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene
diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, dianisidine
diisocyanate, and tetramethylxylylene diisocyanate; alicyclic
diisocyanates such as isophorone diisocyanate,
dicyclohexylmethane-4,4'-diisocyanate, and norbornene diisocyanate;
aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate and
lysine diisocyanate; and mixtures thereof.
[0144] Examples of polyisocyanates include trifunctional or more
highly functional isocyanates such as triphenylmethane
triisocyanate, 1-methylbenzole-2,4,6-triisocyanate,
dimethyltriphenylmethane tetraisocyanate, and mixtures thereof;
modification products such as carbodiimide modification products,
isocyanurate modification products, and biuret modification
products of these trifunctional or more highly functional
isocyanates; block isocyanates resulting from blocking them with
various blocking agents; isocyanurates (trimers) and biuret trimers
of the aforementioned diisocyanates, and the like.
[0145] As the aforementioned anionic group-incorporating polyol,
polyols containing a carboxyl group and/or a sulfonic acid group,
for example, can be used. Specific examples include, but are not
limited to, carboxyl group-containing polyols such as dimethylol
propionic acid, dimethylol butanoic acid, dimethylol butyric acid,
and dimethylol valeric acid; and sulfonic acid group-containing
polyols such as 1,4-butanediol-2-sulfonic acid.
[0146] Basic compounds can be used as neutralizing agents for
anionic groups. Examples include, but are not limited to, ammonia,
basic metal salts, primary amine compounds, secondary amine
compounds, tertiary amine compounds, and the like.
[0147] Various additives in common use may be added as required to
the self-emulsifying type urethane resin of the present invention.
Such additives include, for example, viscosity regulators,
defoaming agents, antioxidants, ultraviolet absorbents,
plasticizers, antistatic agents, and the like.
[0148] To soften the feeling of the textile fiber product, it is
preferable that the glass transition point (Tg) of the
self-emulsifying type urethane resin of the present invention range
from -60 to 20.degree. C. The glass transition point (Tg) more
preferably ranges from -40 to 0.degree. C., still more preferably
from -30 to -10.degree. C.
[0149] The self-emulsifying type urethane resin of the present
invention is intended to bind a pigment to a textile fiber product,
and if the amount blended is large, the fastness improves but the
feeling of the colored portion hardens. Therefore, the amount
blended of the self-emulsifying type urethane resin relative to 100
parts of the aqueous pigment ink of the present invention is
preferably not more than 50 parts, more preferably not more than 30
parts, and still more preferably not more than 20 parts.
[0150] (E) Block Isocyanate Compound
[0151] As the block isocyanate compound in the aqueous pigment ink
in the present invention, one having a group that is reactive with
(C) a water-soluble dispersing agent having a crosslinking property
and (D) a crosslinking functional group in a self-emulsifying type
urethane resin upon heating (e.g., heating at 100.degree. C. or
higher) (e.g., one having 2 or 3 or more such groups) can be
used.
[0152] The block isocyanate compound is preferably a compound
resulting from blocking the isocyanate group in
TMP (trimethylolpropane) adduct form or isocyanurate form of: HDI
(hexamethylene diisocyanate), H6XDI (hydrogenated xylylene
diisocyanate), IPDI (isophorone diisocyanate), or H12MDI
(dicyclohexylmethane diisocyanate). In this case, the blocking
agent is preferably DEM (diethyl malonate), DIPA
(diisopropylamine), TRIA (1,2,4-triazole), DMP
(3,5-dimethylpyrazole), or MEKO (2-butanonoxime), which, however,
are not to be construed as limiting.
[0153] The block isocyanate compound (E) in the present invention
can be used as an oligomer resulting from reacting some of the
isocyanate groups thereof with polyol, polycarbonate, polyester,
polyether, or the like.
[0154] It is preferable that (E) the block isocyanate compound in
the present invention be blended in an aqueous pigment ink after
being rendered water-soluble or self-emulsifying by providing a
hydrophilic group. Thereby the aqueous pigment ink can be made to
be of low viscosity and excellent redispersibility.
[0155] It is desirable that the amount blended of the block
isocyanate compound in the aqueous pigment ink be an amount larger
than the amount that just fits the reacting water-soluble
dispersing agent having a crosslinking property and the number of
crosslinking functional groups in the self-emulsifying type
urethane resin; the amount blended of the block isocyanate compound
relative to 100 parts of the aqueous pigment ink is preferably not
more than 30 parts, more preferably not more than 20 parts, still
more preferably not more than 10 parts. If the amount blended is
larger, the feeling of the textile fiber product can harden, and if
the amount blended is smaller, the color fastness can decrease.
[0156] (F) Pigment
[0157] As a rule, any pigment can be used for the aqueous pigment
ink of the present invention, as far as it is a pigment that can be
used as a coloring material for fiber products, whether an organic
pigment or an inorganic pigment.
[0158] For example, black pigments such as carbon black and iron
oxide black pigment; yellow pigments such as azo pigments,
imidazolone pigments, and titanium yellow pigments; red pigments
such as azo pigments, quinacridone pigments, chromophtal pigments,
diketopyrrolopyrrole pigments, and anthraquinone pigments; blue
pigments such as phthalocyanine pigments; white pigments such as
titanium oxide, aluminum silicate, and silicon oxide; orange
pigments such as indanthrene pigments; purple pigments such as
dioxazine pigments; green pigments such as phthalocyanine pigments;
and the like can be used, which, however, are not to be construed
as limiting.
[0159] (G) Aqueous Liquid
[0160] An aqueous liquid is used as a solvent or dispersion medium
in the aqueous pigment ink.
[0161] As the aqueous liquid, water or a mixture of water and a
water-soluble organic solvent and the like can be used.
[0162] Examples of water-soluble organic solvents include, but are
not limited to:
glycol and glycerin solvents such as ethylene glycol, diethylene
glycol, triethylene glycol, propylene glycol, butylene glycol,
glycerin, and diglycerin as wetting agents; methanol, ethanol,
n-propanol, isopropanol, n-butanol, isobutanol, t-butanol,
2-pyrrolidone, N-methyl-2-pyrrolidone, propylene glycol monomethyl
ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl
ether, methyl ethyl ketone, ethyl acetate, and ethylene glycol
mono-n-butyl ether as surface tension, solubility, or drying speed
regulators; and the like. Such water-soluble organic solvents may
be used alone or in combination of two kinds or more.
[0163] (7) Preparation of Aqueous Pigment Ink
[0164] The aqueous pigment ink in the present invention comprises
at least a pigment, an aqueous liquid as a solvent or dispersion
medium, and:
(C) a water-soluble dispersing agent having a crosslinking
property, (D) a self-emulsifying type urethane resin, and (E) a
block isocyanate compound.
[0165] The aqueous pigment ink in the present invention can be
obtained by, for example, preparing a pigment dispersion from at
least:
(F) a pigment, (G) an aqueous liquid as a solvent or dispersion
medium, and, (C) a water-soluble dispersing agent having a
crosslinking property, and mixing the pigment dispersion and (D) a
self-emulsifying type urethane resin, (E) a block isocyanate
compound, and (G) an aqueous liquid as a solvent or dispersion
medium.
[0166] This pigment dispersion may have a pigment solid content of,
for example, 5 to 40% by weight, which, however, is not to be
construed as limiting.
[0167] The aqueous pigment ink blended with these components can be
rendered an ink that is suitable for inkjet textile printing by,
for example, adjusting the viscosity to a range from 3 to 30 mPas
at 20.degree. C., or adjusting the surface tension to a range from
20 to 40 mN/m, or adjusting both the viscosity and the surface
tension to these ranges, according to the kind and amount of the
aqueous liquid as a solvent or dispersion medium, or the kinds and
amounts of other components.
[0168] Separating coarse pigment particles 500 nm or more in
diameter by filter filtration or centrifugation is preferable for
obtaining an ink that is suitable for inkjet printing.
[0169] In obtaining the aforementioned pigment dispersion, (I) a
dispersing aid may be used to supplement the dispersing
capacity.
[0170] In addition, the aqueous pigment ink in the present
invention may be blended with, in addition to the above-described
components, for example, a thickener, an ultraviolet absorbent, an
antioxidant, a lubricant, a wax, a defoaming agent, an antisetting
agent, a crosslinking catalyst, a chelating agent, a surfactant,
and the like.
[0171] (H) Wet Dispersion Using a Milling Machine
[0172] The above-described pigment dispersion used to prepare the
aqueous pigment ink in the present invention can be obtained by
mixing (F) a pigment, (G) an aqueous liquid as a solvent or
dispersion medium, and (C) a water-soluble dispersing agent having
a crosslinking property, as well as (I) a dispersing aid added as
required, and performing wet dispersion using glass beads, zirconia
beads, titania beads, or the like in a milling machine (beads
mill).
[0173] (I) Dispersing Aid
[0174] In obtaining a pigment dispersion, a dispersing aid can be
used as required. By using an anionic surfactant as a dispersing
aid to supplement the dispersing capacity of (C) a water-soluble
dispersing agent having a crosslinking property, it is possible to
obtain improved dispersion efficiency, pigment particle
micronization, and time-related stability by suppression of
separation, thickening, and the like during storage of the aqueous
pigment ink.
[0175] Examples of anionic surfactants preferred as dispersing aids
include polyoxyethylene styrenated phenyl ether sulfate or
polyoxyethylene alkyl ether sulfate having an HLB of 10 to 16. This
is because a pigment dispersion that has little impact on the color
fastness and excellent long-term storage stability can be obtained.
However, the anionic surfactant that can be used as a dispersing
aid in the present invention is not limited to these examples.
[0176] When using a dispersing aid, the blending ratio (weight) is
preferably not more than 0.3 of the dispersing aid relative to 1 of
pigment. If the ratio of the dispersing aid is more than 0.3, water
resistance reduction can occur.
[0177] (8) Inkjet Printing Machine
[0178] The choice of inkjet printing machine for printing an
aqueous pigment ink by an inkjet process in the printing step is
not particularly limited, but one having a piezo type nozzle head
is preferred. In the case of a thermal type nozzle head, when used
for a long time, the block isocyanate compound in the ink can
undergo thermal cleavage, accelerating the crosslinking reaction.
The piezo type is free from this fear; the ink can be stably
discharged for a long time.
[0179] Examples of such printing machines include, but of course
are not limited to, EPSON PX-V700, EPSON PM-40000PX, Mimaki
TX-16005, FUJIFILM DMP-2831, MASTERMIND MMP8130 (all are trade
names), and the like.
[0180] (9) Heat Treatment Process
[0181] In the method for inkjet textile printing of the present
invention, at least the portion printed with an aqueous pigment ink
of a textile fiber product whose pretreated portion has been
printed with the aqueous pigment ink by an inkjet process in the
printing step is subjected to a heat treatment (e.g., at
100.degree. C. or higher).
[0182] Thereby the block isocyanate compound used in the
pretreatment and/or the block isocyanate compound in the aqueous
pigment ink and the water-soluble dispersing agent having a
crosslinking property and/or the crosslinking functional group in
the self-emulsifying type urethane resin in the aqueous pigment ink
crosslink with each other, whereby they become a water-insoluble
integral entity, and, while in a state containing the pigment, bind
firmly to the fiber in the textile fiber product and pigment-color
the textile fiber product.
[0183] Heating temperature and heating time for the heat treatment
are chosen in view of the heat resistance of the subject textile
fiber product, the characteristics of the substances used for
textile printing, and the like. To achieve sufficient crosslinking,
the block isocyanate compound is required to have a temperature of
not lower than the dissociation reaction temperature thereof, and
the reaction is carried out usually at 100 to 220.degree. C. for 1
to 20 minutes, preferably at 100 to 150.degree. C. for 3 to 10
minutes, still more preferably at 120 to 150.degree. C. for 3 to 5
minutes.
[0184] (10) Post-Treatment
[0185] By performing a post-treatment via an indispensable heat
treatment process for at least the portion printed with an aqueous
pigment ink of a textile fiber product printed with the aqueous
pigment ink by an inkjet process in the printing step, additional
effects can be obtained, such as improved feeling, improved color
fastness, improved slippage, prevention of electrification, and
prevention of discoloration.
[0186] The post-treatment can be performed by applying one kind or
two kinds or more of acrylic resin emulsions, urethane resin
emulsions, crosslinking agents, plasticizers, surfactants,
silicone-based softening agents, and the like (post-treatment
agents) to at least a required portion of the textile fiber product
by padding process, coating process, screen printing process,
inkjet process, spraying process, or the like. These post-treatment
agents may be blended with indispensable additives such as an
antistatic agent, ultraviolet absorbent, antioxidant, defoaming
agent, and drying inhibitor.
EXAMPLES
[0187] The present invention is hereinafter described in further
detail with reference to Examples, to which, however, the present
invention is not limited. Note that "parts" as mentioned in
Examples and elsewhere mean "parts by weight" unless otherwise
stated.
Example 1
Pretreatment Agent 1
[0188] 5 parts of didecyldimethylammonium chloride, 5 parts of
Fixer N (trade name for a block isocyanate compound manufactured by
Matsui Shikiso Chemical Co., Ltd.), and 90 parts of water were
mixed with stirring to yield a pretreatment agent 1.
[0189] <Method of Pretreatment>
[0190] Cotton broadcloth, polyester crepe de chine, and T/C
broadcloth were each padded with the pretreatment agent 1 at a
wringing rate of 60% and then dried at 60.degree. C. for 10 minutes
to yield respective pretreated cloths 1.
[0191] <Water-Soluble Dispersing Agent 1>
[0192] One stirrer, one thermometer, and three dropping funnel were
set to a 1-liter glass flask, 442 parts of water and 15 parts of
AQUARON KH-10 (trade name for a reactive surfactant manufactured by
Dai-ichi Kogyo Seiyaku Co., Ltd.) were placed in the flask, the
atmosphere was replaced with nitrogen with stirring, and the flask
was heated to 60.degree. C.
[0193] Subsequently, various materials were added drop by drop to
the flask:
a mixture of 100 parts of butyl acrylate, 20 parts of ethyl
acrylate, 30 parts of 2-ethylhexyl acrylate, 150 parts of
methacrylic acid, and 21 parts of THIOKALCOL 20 (trade name for a
chain transfer agent manufactured by Kao Corporation) from the
first dropping funnel, an aqueous solution of 3 parts of ammonium
persulfate in 108 parts of distilled water from the second dropping
funnel, and an aqueous solution of 3 parts of sodium hydrogen
sulfite in 108 parts of distilled water from the third dropping
funnel. This dropwise addition was performed concurrently from the
three dropping funnels over 4 hours while keeping the temperature
of the mixture in the flask at 60.degree. C.
[0194] After completion of the dropwise addition, a reaction was
carried out at 60.degree. C. for 1 hour. Subsequently, the reaction
product was allowed to cool down to 20.degree. C. and then filtered
through a wire net to yield an emulsion polymer having a solid
content of 34%. Triethylamine was added to the emulsion polymer to
yield a water-soluble dispersing agent 1 having a pH of 8.2 and a
molecular weight of 8,000.
[0195] <Pigment Dispersion 1>
[0196] 20 parts of a pigment, 6.5 parts of the water-soluble
dispersing agent 1, 50 parts of water, 20 parts of diethylene
glycol, 3 parts of urea, and 0.5 parts of SN-DEFOAMER 777 (trade
name for a defoaming agent manufactured by San Nopco Limited) were
mixed, and this mixture, along with zirconia beads 0.3 mm in
diameter, was applied to a milling machine and dispersed for 1
hour. Thereafter, the zirconia beads were removed, and the
dispersion was filtered through a membrane filter having a pore
diameter of 0.5 .mu.m to yield a pigment dispersion 1.
[0197] Pigment dispersions prepared using as pigments C.I. Pigment
yellow 17, C.I. Pigment Red 122, C.I. Pigment Blue 15:3, and carbon
black, corresponding to yellow, magenta, cyan, and black,
respectively, were named pigment dispersion 1-Y, pigment dispersion
1-M, pigment dispersion 1-C, and pigment dispersion 1-K,
respectively.
[0198] <Aqueous Pigment Ink 1>
[0199] 20 parts of the pigment dispersion 1, 18 parts of glycerin,
20 parts of SUPERFLEX 460 (trade name for a self-emulsifying type
urethane resin manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.),
28 parts of water, and 9 parts of Fixer N were mixed with stirring,
5 parts of water or ethylene glycol was added to obtain a viscosity
of 4 mPas at 20.degree. C. and a surface tension of 32 mN/m,
whereby an aqueous pigment ink 1 was obtained.
[0200] Aqueous pigment inks 1 prepared using the pigment
dispersions 1-Y, 1-M, 1-C, and 1-K were named aqueous pigment inks
1-Y, 1-M, 1-C, and 1-K, respectively.
[0201] For the aqueous pigment inks with various colors obtained,
particle size was measured using a particle size analyzer (trade
name: Microtrac UPA-EX150; manufactured by Nikkiso Co., Ltd.); no
coarse particles having a maximum particle diameter of 500 nm or
more were detected.
[0202] For the various colors of the aqueous pigment inks obtained,
time-related stability at 60.degree. C. for 1 week was examined; no
remarkable change was observed in the viscosity or pigment particle
diameter.
[0203] <Print Evaluation Test>
[0204] The aqueous pigment inks of various colors 1-Y, 1-M, 1-C,
and 1-K were each filled in an inkjet print tester MMP813BT
manufactured by Mastermind K.K., and inkjet-printed on each
pretreated cloth 1; thereafter, the printed cloths were dried at
60.degree. C. for 10 minutes and heated at 150.degree. C. for 3
minutes; colored cloths without bleeding and with high brilliancy,
high color density, and soft feeling were obtained.
[0205] <Print Stability Test>
[0206] The aqueous pigment inks of various colors 1-Y, 1-M, 1-C,
and 1-K were each filled in an inkjet print tester MMP813BT
manufactured by Mastermind K.K., and continuously printed on each
pretreated cloth 1 for 10 minutes; good discharge stability and
print stability were exhibited without defective pixels, print
irregularity, and the like.
[0207] Thereafter, the inkjet print tester was stopped, and while
in a state filled in the inkjet print tester, the aqueous pigment
inks of various colors were allowed to stand at room temperature
for 1 week; thereafter, head cleaning was performed, and the inks
were continuously printed on each pretreated cloth 1 for 10
minutes; good discharge stability and print stability were
exhibited without defective pixels, print irregularity, and the
like as before the standing.
[0208] <Washing Fastness Test>
[0209] The colored cloths obtained were subjected to a washing
fastness test in accordance with the JIS L-0217 103 method.times.5
times (5-grade rating method); good color fastness to washing was
exhibited: grade 4 for all of cotton broadcloth, polyester crepe de
chine, and T/C broadcloth.
[0210] <Test for Color Fastness to Rubbing>
[0211] The colored cloths obtained were subjected to a test for
color fastness to rubbing in accordance with the JIS L-0849 test
for color fastness to rubbing (5-grade rating method); good
fastness to rubbing was exhibited: grade 4 for all of cotton
broadcloth, polyester crepe de chine, and T/C broadcloth in dry
rubbing, and grade 3-4 for cotton broadcloth and T/C broadcloth and
grade 3 for polyester crepe de chine in wet rubbing.
Example 2
Pretreatment Agent 2
[0212] 5 parts of distearyldimethylammonium chloride, 5 parts of
Fixer N, and 90 parts of water were mixed with stirring to yield a
pretreatment agent 2.
[0213] <Method of Pretreatment>
[0214] Cotton broadcloth, polyester crepe de chine, and T/C
broadcloth were each padded with the pretreatment agent 2 and then
dried at 60.degree. C. for 10 minutes in the same manner as Example
1 to yield respective pretreated cloths 2.
[0215] <Water-Soluble Dispersing Agent 2>
[0216] Starting materials were treated in the same manner as the
obtainment of a water-soluble dispersing agent 1 in Example 1
except that the monomers in the first dropping funnel were replaced
with 140 parts of butyl acrylate, 20 parts of ethyl acrylate, 30
parts of 2-ethylhexyl acrylate, 80 parts of methacrylic acid, 10
parts of acrylic acid, and 20 parts of hydroxyethyl acrylate, to
yield a water-soluble dispersing agent 2 having a pH of 8.2 and a
molecular weight of 7,000.
[0217] <Pigment Dispersion 2>
[0218] 20 parts of pigment, 28 parts of water-soluble dispersing
agent 2, 48.5 parts of water, 20 parts of diethylene glycol, 3
parts of urea, and 0.5 parts of SN-DEFOAMER 777 were mixed, and
this mixture, along with zirconia beads 0.3 mm in diameter, was
applied to a milling machine and dispersed for 1 hour. Thereafter,
the zirconia beads were removed, and the dispersion was filtered
through a membrane filter with a pore diameter of 0.5 .mu.m to
yield a pigment dispersion 2.
[0219] Pigment dispersions were prepared using the same pigments
corresponding to yellow, magenta, cyan, and black as in Example 1,
and named pigment dispersions 2-Y, 2-M, 2-C, and 2-K,
respectively.
[0220] <Aqueous Pigment Ink 2>
[0221] 20 parts of the pigment dispersion 2, 18 parts of glycerin,
20 parts of PERMARIN UA-300 (trade name for a self-emulsifying type
urethane resin manufactured by Sanyo Chemical Industries, Ltd.), 28
parts of water, and 9 parts of Fixer N were mixed with stirring,
and 5 parts of water or ethylene glycol was added to obtain a
viscosity of 5 mPas at 20.degree. C. and a surface tension of 33
mN/m, whereby an aqueous pigment ink 2 was obtained.
[0222] Aqueous pigment inks 2 prepared using the pigment
dispersions 2-Y, 2-M, 2-C, and 2-K were named aqueous pigment inks
2-Y, 2-M, 2-C, and 2-K, respectively.
[0223] For the aqueous pigment inks with various colors obtained,
particle size was measured in the same manner as Example 1; no
coarse particles having a maximum particle diameter of 500 nm or
more were detected.
[0224] For the various colors of the aqueous pigment inks obtained,
time-related stability at 60.degree. C. for 1 week was examined; no
remarkable change was observed in the viscosity or pigment particle
diameter.
[0225] <Print Evaluation Test>
[0226] The aqueous pigment inks 2-Y, 2-M, 2-C, and 2-K were
subjected to a print evaluation test on the pretreated cloth 2 in
the same manner as Example 1; colored cloths without bleeding and
with high brilliancy, high color density, and soft feeling were
obtained.
[0227] <Print Stability Test>
[0228] The aqueous pigment inks 2-Y, 2-M, 2-C, and 2-K were
subjected to a print stability test using the pretreated cloth 2 in
the same manner as Example 1; good discharge stability and print
stability were exhibited both before and after they were allowed to
stand.
[0229] <Washing Fastness Test>
[0230] The colored cloths obtained were subjected to a washing
fastness test in the same manner as Example 1; good color fastness
to washing was exhibited: grade 4 for all of cotton broadcloth,
polyester crepe de chine, and T/C broadcloth.
[0231] <Test for Color Fastness to Rubbing>
[0232] The colored cloths obtained were subjected to a test for
color fastness to rubbing in the same manner as Example 1; good
color fastness to rubbings was exhibited: grade 4 for all of cotton
broadcloth, polyester crepe de chine, and T/C broadcloth in dry
rubbing, and grade 3-4 for cotton broadcloth and T/C broadcloth and
grade 3 for polyester crepe de chine in wet rubbing.
Example 3
Pretreatment Agent 3
[0233] 5 parts of didecyldimethylammonium chloride, 5 parts of
AQB-102 (trade name for a block isocyanate compound manufactured by
Nippon Polyurethane Industry Co., Ltd.), and 90 parts of water were
mixed with stirring to yield a pretreatment agent 3.
[0234] <Method of Pretreatment>
[0235] Cotton broadcloth, polyester crepe de chine, and T/C
broadcloth were each padded with the pretreatment agent 3 and then
dried at 60.degree. C. for 10 minutes in the same manner as Example
1 to yield respective pretreated cloths 3.
[0236] <Aqueous Pigment Ink 3>
[0237] 20 parts of the pigment dispersion 1 of Example 1, 18 parts
of glycerin, 20 parts of PERMARIN UA-300, 28 parts of water, and 9
parts of AQB-102 were mixed with stirring, 5 parts of water or
ethylene glycol was added to obtain a viscosity of 5 mPas at
20.degree. C. and a surface tension of 32 mN/m, whereby an aqueous
pigment ink 3 was obtained.
[0238] Aqueous pigment inks 3 prepared using the pigment
dispersions 1-Y, 1-M, 1-C, and 1-K were named aqueous pigment inks
3-Y, 3-M, 3-C, and 3-K, respectively.
[0239] For the aqueous pigment inks with various colors obtained,
particle size was measured in the same manner as Example 1; no
coarse particles having a maximum particle diameter of 500 nm or
more were detected.
[0240] For the various colors of the aqueous pigment inks obtained,
time-related stability at 60.degree. C. for 1 week was examined; no
remarkable change was observed in the viscosity or pigment particle
diameter.
[0241] <Print Evaluation Test>
[0242] The aqueous pigment inks 3-Y, 3-M, 3-C, and 3-K were
subjected to a print evaluation test on the pretreated cloth 3 in
the same manner as Example 1; colored cloths without bleeding and
with high brilliancy, high color density, and soft feeling were
obtained.
[0243] <Print Stability Test>
[0244] The aqueous pigment inks 3-Y, 3-M, 3-C, and 3-K were
subjected to a print stability test using the pretreated cloth 3 in
the same manner as Example 1; good discharge stability and print
stability were exhibited both before and after the inks were
allowed to stand.
[0245] <Washing Fastness Test>
[0246] The colored cloths obtained were subjected to a washing
fastness test in the same manner as Example 1; good color fastness
to washing was exhibited: grade 4 for all of cotton broadcloth,
polyester crepe de chine, and T/C broadcloth.
[0247] <Test for Color Fastness to Rubbing>
[0248] The colored cloths obtained were subjected to a test for
color fastness to rubbing in the same manner as Example 1; good
color fastness to rubbings was exhibited: grade 4 for all of cotton
broadcloth, polyester crepe de chine, and T/C broadcloth in dry
rubbing, and grade 3-4 for cotton broadcloth and T/C broadcloth and
grade 3 for polyester crepe de chine in wet rubbing.
Example 4
Pigment Dispersion 3
[0249] 20 parts of a pigment, 6.5 parts of the water-soluble
dispersing agent 2 of Example 2, 6 parts of HITENOL NF13
(dispersing aid: trade name for an anionic surfactant manufactured
by Dai-ichi Kogyo Seiyaku Co., Ltd.), 44 parts of water, 20 parts
of diethylene glycol, 3 parts of urea, and 0.5 parts of SN-DEFOAMER
777 were mixed, and this mixture, along with zirconia beads 0.3 mm
in diameter, was applied to a milling machine and dispersed for 1
hour. Thereafter, the zirconia beads were removed, and the
dispersion was filtered through a membrane filter with a pore
diameter of 0.5 .mu.m to yield a pigment dispersion 3.
[0250] Pigment dispersions were prepared using the same pigments
corresponding to yellow, magenta, cyan, and black as in Example 1,
and named pigment dispersions 3-Y, 3-M, 3-C, and 3-K,
respectively.
[0251] <Aqueous Pigment Ink 4>
[0252] 20 parts of the pigment dispersion 3, 18 parts of glycerin,
20 parts of SUPERFLEX 460, 28 parts of water, and 9 parts of Fixer
N were mixed with stirring, and 5 parts of water or ethylene glycol
were added to obtain a viscosity of 5 mPas at 20.degree. C. and a
surface tension of 31 mN/m, whereby an aqueous pigment ink 4 was
obtained.
[0253] Aqueous pigment inks 4 prepared using the pigment
dispersions 3-Y, 3-M, 3-C, and 3-K were named aqueous pigment inks
4-Y, 4-M, 4-C, and 4-K, respectively.
[0254] For the aqueous pigment inks with various colors obtained,
particle size was measured in the same manner as Example 1; no
coarse particles having a maximum particle diameter of 500 nm or
more were detected.
[0255] For the various colors of the aqueous pigment inks obtained,
time-related stability at 60.degree. C. for 1 week was examined; no
remarkable change was observed in the viscosity or pigment particle
diameter.
[0256] <Print Evaluation Test>
[0257] The aqueous pigment inks 4-Y, 4-M, 4-C, and 4-K were
subjected to a print evaluation test on the pretreated cloth 1 in
the same manner as Example 1; colored cloths without bleeding and
with high brilliancy, high color density, and soft feeling were
obtained.
[0258] <Print Stability Test>
[0259] The aqueous pigment inks 4-Y, 4-M, 4-C, and 4-K were
subjected to a print stability test using the pretreated cloth 1 in
the same manner as Example 1; good discharge stability and print
stability were exhibited both before and after the inks were
allowed to stand.
[0260] <Washing Fastness Test>
[0261] The colored cloths obtained were subjected to a washing
fastness test in the same manner as Example 1; good color fastness
to washing was exhibited: grade 4 for all of cotton broadcloth,
polyester crepe de chine, and T/C broadcloth.
[0262] <Test for Color Fastness to Rubbing>
[0263] The colored cloths obtained were subjected to a test for
color fastness to rubbing in the same manner as Example 1; good
color fastness to rubbings was exhibited: grade 4 for all of cotton
broadcloth, polyester crepe de chine, and T/C broadcloth in dry
rubbing, and grade 3 for cotton broadcloth and T/C broadcloth and
grade 2-3 for polyester crepe de chine in wet rubbing.
Example 5
Method of Pretreatment
[0264] Black cotton broadcloth was padded with the pretreatment
agent 1 and then dried at 60.degree. C. for 10 minutes in the same
manner as Example 1 to yield a pretreated cloth 5.
[0265] <Pigment Dispersion 5>
[0266] Starting materials were treated in the same manner as
Example 1 except that titanium oxide was used as a pigment, to
yield a pigment dispersion 5-W.
[0267] <Aqueous Pigment Ink 5>
[0268] 50 parts of the pigment dispersion 5-W, 18 parts of
glycerin, 10 parts of SUPERFLEX 460, 12 parts of water, and 5 parts
of Fixer N were mixed with stirring, and 5 parts of water or
ethylene glycol was added to obtain a viscosity of 5 mPas at
20.degree. C. and a surface tension of 32 mN/m, whereby an aqueous
pigment ink 5-W was obtained.
[0269] For the aqueous pigment ink 5-W obtained, particle size was
measured in the same manner as Example 1; no coarse particles
having a maximum particle diameter of 500 nm or more were
detected.
[0270] For the aqueous pigment ink 5-W obtained, time-related
stability at 60.degree. C. for 1 week was examined; no remarkable
change was observed in the viscosity or pigment particle
diameter.
[0271] <Print Evaluation Test>
[0272] The aqueous pigment ink 5-W was filled in an inkjet print
tester MMP813BT, and inkjet-printed on the pretreated cloth 5 to
form a white masking layer. The aqueous pigment inks 1-Y, 1-M, 1-C,
and 1-K were inkjet-printed on the white masking layer in the same
manner as Example 1, thereafter, the cloth was dried at 60.degree.
C. for 10 minutes and heated at 150.degree. C. for 3 minutes;
colored cloths without bleeding and with high brilliancy, high
color density, and soft feeling were obtained.
[0273] <Washing Fastness Test>
[0274] The colored cloths obtained were subjected to a washing
fastness test in the same manner as Example 1; good color fastness
to washing was exhibited at grade 4.
[0275] <Test for Color Fastness to Rubbing>
[0276] The colored cloths obtained were subjected to a test for
color fastness to rubbing in the same manner as Example 1; good
color fastness to rubbings was exhibited: grade 3-4 in dry rubbing
and grade 3 in wet rubbing.
Example 6
Post-Treatment
[0277] The various colored cloths of Example 1 to 5 were each
padded with a post-treatment agent consisting of 5 parts of Fixer
N, 3 parts of Faster XA (trade name for an acrylic resin emulsion
manufactured by Matsui Shikiso Chemical Co., Ltd.), 5 parts of
Abrasion XF (trade name for a silicone-based softening agent
manufactured by Matsui Shikiso Chemical Co., Ltd.), and 87 parts of
water at a wringing rate of 65%, and dried at 60.degree. C. for 10
minutes and then heated at 150.degree. C. for 3 minutes.
[0278] The post-treated cloths obtained were tested in the same
manner as the washing fastness test and test for color fastness to
rubbing performed in the various Examples; various properties of
fastness improved by about 0.5 grades compared with
non-post-treated colored cloths, and the feeling became softer.
Comparative Example 1
[0279] The aqueous pigment inks 1-Y, 1-M, 1-C, and 1-K were
subjected to a print evaluation test in the same manner as Example
1 except that no pretreatment was performed; the colored cloths
obtained had unsatisfactory quality with severe bleeding and poor
brilliancy.
Comparative Example 2
Pretreatment Agent NG1
[0280] 5 parts of didecyldimethylammonium chloride and 95 parts of
water were mixed with stirring to yield a pretreatment agent
NG1.
[0281] <Method of Pretreatment>
[0282] Cotton broadcloth, polyester crepe de chine, and T/C
broadcloth were each padded with the pretreatment agent NG1 and
then dried at 60.degree. C. for 10 minutes in the same manner as
Example 1 to yield respective pretreated cloths NG1.
[0283] <Print Evaluation Test>
[0284] The aqueous pigment inks 1-Y, 1-M, 1-C, and 1-K were
subjected to a print evaluation test on the pretreated cloths NG1
in the same manner as Example 1; colored cloths without bleeding
and with high brilliancy, high color density, and soft feeling were
obtained.
[0285] <Washing Fastness Test>
[0286] The colored cloths obtained were subjected to a washing
fastness test in the same manner as Example 1; the washing fastness
was worse than in Example 1: grade 3 for all of cotton broadcloth,
polyester crepe de chine, and T/C broadcloth.
[0287] <Test for Color Fastness to Rubbing>
[0288] The colored cloths obtained were subjected to a test for
color fastness to rubbing in the same manner as Example 1; the
color fastness to rubbing was worse than in Example 1: grade 3 for
all of cotton broadcloth, polyester crepe de chine, and T/C
broadcloth in dry rubbing, and grade 2-3 for cotton broadcloth and
T/C broadcloth and grade 2 for polyester crepe de chine in wet
rubbing.
Comparative Example 3
Pretreatment Agent NG2
[0289] 5 parts of Fixer N and 95 parts of water were mixed with
stirring to yield a pretreatment agent NG2.
[0290] <Method of Pretreatment>
[0291] Cotton broadcloth, polyester crepe de chine, and T/C
broadcloth were each padded with the pretreatment agent NG2 and
then dried at 60.degree. C. for 10 minutes in the same manner as
Example 1 to yield respective pretreated cloths NG2.
[0292] <Print Evaluation Test>
[0293] The aqueous pigment inks 1-Y, 1-M, 1-C, and 1-K were
subjected to a print evaluation test on the pretreated cloths NG2
in the same manner as Example 1; the colored cloths had
unsatisfactory quality with severe bleeding and poor
brilliancy.
Comparative Example 4
Pretreatment Agent NG3
[0294] 5 parts of lauryltrimethylammonium chloride, 5 parts of
Fixer N, and 90 parts of water were mixed with stirring to yield a
pretreatment agent NG3.
[0295] <Method of Pretreatment>
[0296] Cotton broadcloth, polyester crepe de chine, and T/C
broadcloth were each padded with the pretreatment agent NG3 and
then dried at 60.degree. C. for 10 minutes in the same manner as
Example 1 to yield respective pretreated cloths NG3.
[0297] <Print Evaluation Test>
[0298] The aqueous pigment inks 1-Y, 1-M, 1-C, and 1-K were
subjected to a print evaluation test on the pretreated cloths NG3
in the same manner as Example 1; colored cloths without bleeding
and with high brilliancy, high color density, and soft feeling were
obtained.
[0299] <Washing Fastness Test>
[0300] The colored cloths obtained were subjected to a washing
fastness test in the same manner as Example 1; the washing fastness
was worse than in Example 1: grade 3 for all of cotton broadcloth,
polyester crepe de chine, and T/C broadcloth.
[0301] <Test for Color Fastness to Rubbing>
[0302] The colored cloths obtained were subjected to a test for
color fastness to rubbing in the same manner as Example 1; the
color fastness to rubbing was worse than in Example 1: grade 3-4
for all of cotton broadcloth, polyester crepe de chine, and T/C
broadcloth in dry rubbing, and grade 2-3 for cotton broadcloth and
T/C broadcloth and grade 2 for polyester crepe de chine in wet
rubbing.
Comparative Example 5
Pretreatment Agent NG4
[0303] 5 parts of SAFTOMER ST-3300 (trade name for a cationic
acrylic resin manufactured by Mitsubishi Chemical Corporation), 5
parts of Fixer N, and 90 parts of water were mixed with stirring to
yield a pretreatment agent NG4.
[0304] <Method of Pretreatment>
[0305] Cotton broadcloth, polyester crepe de chine, and T/C
broadcloth were each padded with the pretreatment agent NG4 and
then dried at 60.degree. C. for 10 minutes in the same manner as
Example 1 to yield respective pretreated cloths NG4.
[0306] <Print Evaluation Test>
[0307] The aqueous pigment inks 1-Y, 1-M, 1-C, and 1-K were
subjected to a print evaluation test on the pretreated cloths NG4
in the same manner as Example 1; colored cloths of unsatisfactory
quality with slight bleeding, slightly poor brilliancy, low color
density, and hard feeling were obtained.
Comparative Example 6
Water-Soluble Dispersing Agent NG1
[0308] Starting materials were treated in the same manner as the
obtainment of a water-soluble dispersing agent 1 in Example 1
except that the monomers in the first dropping funnel were replaced
with 50 parts of butyl acrylate and 250 parts of methacrylic acid,
to yield a water-soluble dispersing agent NG1 having a pH of 8.1
and a molecular weight of 7,500.
[0309] <Pigment Dispersion NG1>
[0310] 20 parts of a pigment, 6.5 parts of the water-soluble
dispersing agent NG1, 50 parts of water, 20 parts of diethylene
glycol, 3 parts of urea, and 0.5 parts of SN-DEFOAMER 777 were
mixed, and this mixture, along with zirconia beads 0.3 mm in
diameter, was applied to a milling machine and dispersed for 1
hour; the pigment dispersion obtained was found to be highly
viscous and unusable for obtaining the aqueous pigment ink in the
present invention.
Comparative Example 7
Pigment Dispersion NG2
[0311] 20 parts of a pigment, 7 parts of EMULGEN 108 (trade name
for a nonionic surfactant manufactured by Kao Corporation), 49.5
parts of water, 20 parts of diethylene glycol, 3 parts of urea, and
0.5 parts of SN-DEFOAMER 777 were mixed, and this mixture, along
with zirconia beads 0.3 mm in diameter, was applied to a milling
machine and dispersed for 1 hour. Thereafter, the zirconia beads
were removed, and the dispersion was filtered through a membrane
filter having pore diameter of 0.5 .mu.m to yield a pigment
dispersion NG2.
[0312] Pigment dispersions were prepared using the same pigments
corresponding to yellow, magenta, cyan, and black as in Example 1,
and named pigment dispersions NG2-Y, NG2-M, NG2-C, and NG2-K,
respectively.
[0313] <Aqueous Pigment Inks NG1>
[0314] Starting materials were treated in the same manner as
Example 1 except that the pigment dispersions 1-Y, 1-M, 1-C, and
1-K were replaced with the pigment dispersions NG2-Y, NG2-M, NG2-C,
and NG2-K, to yield aqueous pigment inks NG1-Y, NG1-M, NG1-C, and
NG1-K.
[0315] The pretreated cloth 1 was inkjet-printed in the same manner
as Example 1 except that the aqueous pigment inks 1-Y, 1-M, 1-C,
and 1-K were replaced with the aqueous pigment inks NG1-Y, NG1-M,
NG1-C, and NG1-K, and the colored cloths obtained were subjected to
a washing fastness test and test for color fastness to rubbing in
the same manner as Example 1; the results were worse than in
Example 1: grade 2 of washing fastness for all pretreated cloths 1
and grade 3 of color fastness to rubbing for all cloths in dry
rubbing and grade 2 for cotton broadcloth and T/C broadcloth in wet
rubbing.
Comparative Example 8
Aqueous Pigment Inks NG2
[0316] Starting materials were treated in the same manner as
Example 2 except that PERMARIN UA-300 in the aqueous pigment ink 2
was replaced with SUPERFLEX E-4800 (forcibly emulsified urethane
resin manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), to yield
aqueous pigment inks NG2-Y, NG2-M, NG2-C, and NG2-K.
[0317] For the aqueous pigment inks with various colors obtained,
particle size was measured in the same manner as Example 1; no
coarse particles having a maximum particle diameter of 500 nm or
more were detected.
[0318] However, for the various colors of the aqueous pigment inks
obtained, time-related stability at 60.degree. C. for 1 week was
examined; the viscosity increased, and coarse particles 500 nm or
more in diameter were detected.
[0319] The aqueous pigment inks NG2-Y, NG2-M, NG2-C, and NG2-K were
subjected to a print stability test using the pretreated cloth 2 in
the same manner as Example 1; defective pixels and print
irregularity due to drying were seen, and the print stability was
poor. Furthermore, the inkjet print tester was stopped, and, while
in a state filled in the inkjet print tester, the aqueous pigment
inks were allowed to stand at room temperature for 1 week;
thereafter, the inkjet print tester did not restore the capability
of satisfactory inkjet printing, and stable discharge was not
achieved, even after head cleaning was performed.
Comparative Example 9
Aqueous Pigment Inks NG3
[0320] Starting materials were treated in the same manner as
Example 2 except that Fixer N in the aqueous pigment ink 2 was
replaced with water, to yield aqueous pigment inks NG3-Y, NG3-M,
NG3-C, NG3-K.
[0321] The pretreated cloth 1 was inkjet-printed in the same manner
as Example 1 except that the aqueous pigment inks 1-Y, 1-M, 1-C,
and 1-K were replaced with the aqueous pigment inks NG3-Y, NG3-M,
NG3-C, and NG3-K, and the colored cloths obtained were subjected to
a washing fastness test and a test for color fastness to rubbing in
the same manner as Example 1; the results were worse than in
Example 1: grade 2-3 of washing fastness for all pretreated cloths
1, and grade 3-4 of color fastness to rubbing for all cloths in dry
rubbing and grade 2-3 for cotton broadcloth and T/C broadcloth in
wet rubbing.
[0322] The above-described results of Examples and Comparative
Examples revealed that the constituent components of (A) a
quaternary ammonium salt type cationic surfactant represented by
the formula (1), (B) a block isocyanate compound, (C) a
water-soluble dispersing agent having a crosslinking property, (D)
a self-emulsifying type urethane resin, and (E) a block isocyanate
compound in the present invention are of particular
significance.
* * * * *